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JOURNAL OF CHEMICAL PHYSICS

VOLUME 109, NUMBER 14

8 OCTOBER 1998

Fourier transform emission spectroscopy of the A of BeH
C. Focsa,a) S. Firth,b) P. F. Bernath,c) and R. Colin

2

– X2

system

´ ´ Laboratoire de Chimie Physique Moleculaire, Universite Libre de Bruxelles, C.P. 160/09, 50 av. F. D. Roosevelt, 1050-Brussels, Belgium

Received 21 May 1998; accepted 2 July 1998 transition of BeH was observed by Fourier transform emission spectroscopy The A 2 – X 2 using a hollow cathode discharge lamp. The 0–0 to 6–6 bands were rotationally analyzed and molecular constants extracted. The equilibrium rotational constants B e and bond lengths were found to be 10.331 21 50 cm 1 and 1.341 68 3 Å for the ground state and 10.466 31 27 cm 1 and 1.332 99 2 Å in the excited state. In order to link the diagonal bands together and to determine the vibrational constants, the 0–1 to 6–7 bands in an archival arc emission spectrum were also and A 2 states, the spectroscopic constants are nearly identical rotationally analyzed. In the X 2 so the v 1 bands were too weak to be seen in our Fourier transform spectra. Franck–Condon transition from Rydberg–Klein–Rees potential factors were calculated for the A 2 – X 2 curves. These new rotational analyses now link up with the previous work on the 0–7, 0–8, 0–9, ` –X 2 system R. Colin, C. Dreze, and M. Steinhauer, Can. J. 1–9 and 1–10 bands of the C 2 Phys. 61, 641 1983 . Spectroscopic data are thus available for all bound ground state vibrational levels, v 0 – 10, and a set of Dunham Y constants were determined. BeH joins the small group of chemically bound molecules for which a nearly complete set of ground state rovibronic energy levels are known experimentally. © 1998 American Institute of Physics. S0021-9606 98 00238-4

I. INTRODUCTION

The light BeH molecule has been extensively studied by ab initio quantum chemists and serves as a test case for open-shell systems e.g., Refs. 1–9 . Partly because of the toxicity of the Be-containing molecules, BeH has been less popular with experimentalists. Watson10 and Olsson11 carried out early work on the electronic emission spectra of BeH in the late 1920s and early 1930s. BeH was made by running an arc discharge with Be electrodes in an atmosphere of hydrogen. This early work provided extensive spectra of the system and some data for the B 2 – X 2 A 2 –X 2 system, but of only moderate quality.10–13 Koontz14 recorded transition of BeD and this system has the A 2 – X 2 been detected recently in emission from the plasma confined in a tokamak.15 The work of Colin and co-workers16–21 has improved and expanded our spectroscopic knowledge of BeH and BeD and they were even able to study BeT. Improved spectra were recorded by using a carbon tube furnace King furnace instead of an arc, and by measuring the bands in absorption. In this way visible, UV, and vacuum UV VUV down to
a

Permanent address: Laboratoire de Physique des Lasers, Atomes et Mol´ ecules, UMR CNRS, Centre d’Etudes et de Recherches Lasers et Applica´ tions, Universite des Sciences et Technologies de Lille, 59 655 Villeneuve d’Ascq Cedex, France. b Present address: Department of Chemistry, University College London, 20 Gordon St., London WC1H0A6, United Kingdom. c Author to whom correspondence should be addressed. Permanent address: Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada. 0021-9606/98/109(14)/5795/8/$15.00 5795

1700 Å spectra of BeH and BeD were recorded with the 10 m spectrograph at the National Research Council in Ottawa.16 These photographic plates allowed a reanalysis of system and for the assignment of the the A 2 – X 2 VUV systems.19 For reasons of safety the A 2 – X 2 transition of BeT was recorded in a hollow cathode lamp with a 2 m spectrograph.18 Most recently, the 3d Rydberg complex of BeH and BeD was analyzed.21 All of the known band systems of BeH, BeD, and BeT –X 2 sysare very diagonal except for the weak C 2 tem that can only be seen in emission from an arc discharge.20 In addition to the 0–0 to 5–5 bands of the system, the arc produced the 0–7, 0–8, 0–9, A 2 –X 2 –X 2 system.20 1–9, 2–9, and 1–10 bands of the C 2 The tentative identification of the 0–6 band in this work state correlates to the proved to be incorrect. The C 2 3 2 same Be ( P) H( S) asymptote as the A 2 state but has a r e 2.301 Å compared to r e 1.333 Å for the A 2 state state see Fig. 1 of Ref. 20 . and r e 1.342 Å for the X 2 The problem is that the very weak off-diagonal bands of the system only partly link the v and v 0 – 5 A 2 –X 2 vibrational levels together and there is no direct connection –X 2 bands and any of the other between the C 2 known ground state vibrational levels ( v 0 – 5) in BeH. states perturb each Fortunately, the A 2 and the C 2 other20 so that an indirect connection could be made and the state could be located relative v 7 – 10 levels of the X 2 to v 0. The dissociation energy (D e 17 426 100 cm 1) is state from the limiting curve of known for the X 2
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predissociation20 and from predissociation in the B 2 state.19 The v 10 level turns out to be the last bound vistate, although v 11 may be brational level of the X 2 bound by a few cm 1. BeH is thus a rather unique system that has spectroscopic data for low vibrational levels ( v 0 – 5, not all linked and high vibrational levels ( v 7 – 10). If these ground state levels could all be directly linked together and the v 6 gap filled, then the experimental data for BeH would be much more useful. With only five electrons BeH is already widely used to benchmark openshell ab initio methods and to study the breakdown of the Born–Oppenheimer approximation.8,18 We report here new Fourier transform emission spectra transition for the 0–0 to 6–6 vibraof the A 2 – X 2 tional bands. An attempt was made to link these bands together by observing the vibration–rotation bands as well as the v 1 bands of the A – X system by Fourier transform emission spectroscopy, but without success. Our hollow 1 bands and cathode source was too weak to see the v strong thermal emission from the cathode swamped the infrared vibration–rotation emission bands. There is, however, an infrared spectrum of BeH isolated in an argon matrix.22 We, therefore, used unpublished data from the same arc spectrum used for the C 2 –X 2 analysis20 2 and identified the 0–1 to 6–7 bands of the A –X 2 2 system. Thus the v 0 – 10 levels in the X state and v 0 – 6 in the A 2 state are now linked together on the same energy scale. BeH thus joins the very small and exclusive group of chemically bound molecules that includes H2) for which all of the bound ground state levels are known experimentally.
II. EXPERIMENTAL DETAILS

The A 2 – X 2 v 0 sequence of BeH was excited in a Be hollow cathode discharge and recorded using a Fourier transform spectrometer. Spectra from two different types of hollow cathode discharge lamps were recorded. In the first experiment, we used a water-cooled Be cathode held inside a brass collar and a tungsten ring anode. The cooling water was either off or flowing very slowly. The cathode was operated at currents of 1.2 A the maximum that we could get without arcing and with total pressures of a few Torr with a mixture of 1% H2 in Ne. Be does not sputter well and the cathode must be very hot to evaporate sufficient metal to make BeH. The Doppler width for well-resolved BeH lines in this relatively cool spectrum was typically 0.15 cm 1, corresponding to a temperature of about 1200 K. In the second experiment, we recorded a hotter spectrum by using a classical, uncooled Be hollow cathode discharge lamp and with He as the buffer gas. This cathode was not bored through and a tungsten pin anode was used. In this case, the current was 0.7 A and the total pressure was 8 Torr with 20% H2 and 80% He in the nonflowing gas mixture. The BeH rotational lines observed on this second spectrum had measured linewidths of 0.19 cm 1 corresponding to a temperature of about 1500 K. Our best spectrum was recorded just before the cathode melted. The combined study of the two spectra proved to be very useful: while the cooler

spectrum provided better resolved lines, the hotter one allowed us to extend the assignment of the branches to higher N values. The emission from the discharge was recorded with a Bruker IFS 120 HR Fourier transform spectrometer. A Si photodiode detector was used and a bandpass filter served to isolate the 18 000–22 500 cm 1 spectral region. A total of 50 scans were coadded in about 30 min of observation at an instrumental resolution of 0.1 cm 1. Higher resolution spectra were not recorded because of the large Doppler broadening of the BeH lines. The isolated BeH lines were not always symmetric because of problems with the phase correction. The spectra were recorded in air so the line positions were first corrected to vacuum wave numbers using the refractive index of air. The wave number scale was then calibrated in the cooler spectrum using Ne lines23 and this calibration was transferred to the hotter spectrum using strong BeH lines. The estimated absolute accuracy of the wave number scale is 0.003 cm 1. The line positions were measured by fitting Voigt line shape functions to the experimental lines in a nonlinear, least-squares procedure using the program SPECTRA. The precision of our measurements is estimated to be about 0.01 cm 1 for unblended lines. The experimental setup used to record the A 2 – X 2 1 sequence was previously described in detail by v Colin et al.20 in their study of the C 2 –X 2 system and only a brief description will be given here. A conventional arc source with Be electrodes was used to excite the spectrum. The dc arc was operated at 190 V and 9 A, with a 1:5 mixture of H2 and Ar at a total pressure of a few Torr. The emission spectra were photographed in the second order of a 2 m Czerny–Turner grating spectrograph using Kodak I-F plates and 50 m slits. The emission spectrum of an iron hollow cathode was used for wavelength calibration. The absolute error in the line positions is estimated to be 0.2 cm 1 and the uncertainty in the relative line positions is 0.1 cm 1 for strong unblended lines.20
III. ANALYSIS A. Description of the observed bands

An overview of the Fourier transform FT emission spectrum of the A 2 – X 2 v 0 sequence of BeH is presented in Fig. 1. The 0–0 to 6–6 bands could be identified in our new spectra. The detection of the 6–6 band is new and the Q lines of the 4–4 and 5–5 bands were also seen for the first time. For the 0–0 to 5–5 bands, the number of assigned lines was extended to both higher and lower N values compared to the previous analyses.16,20 Some weak and irregular structure was seen near 20 008 cm 1 that is probably the 7–7 Q head but no rotational assignments could be made. All the observed bands have six branches, P 1 , P 2 , Q 1 , Q 2 , R 1 and R 2 , with the doublet fine structure splitting (F 1 and F 2 ) resolved at low N values up to N 12 in the case of the cooler spectrum as appropriate for a Hund’s case b 2 –2 transition. As noted first by Watson in 1928, the P, Q, and R branches are very peculiar because a head forms at high N in all three branches. BeH is, therefore, cited in Herzberg24 as an example of molecule that has ‘‘extra’’

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FIG. 1. An overview of the A 2 – X 2 emission spectrum of BeH recorded with a Fourier transform spectrometer.

FIG. 2. The 6–6 Q branch of the A 2 – X 2 transition of BeH showing unusual rotational structure. The two lines marked with asterisks are from other bands.

heads. In our hollow cathode spectra, R heads were observed for the 0–0 and 1–1 bands, and ‘‘extra’’ Q heads found for the 0–0, 1–1, 2–2 and 3–3 bands the 4–4, 5–5, and 6–6 Q branches exhibit particularly odd features that will be discussed below . The A 2 – X 2 v 0 sequence also presents a ‘‘vibrational head’’ or ‘‘head-of-heads’’ for the Q branches. The origins of the vibrational bands go initially to higher wave numbers with T 00 20 030.963 cm 1, T 11 20 051.310 cm 1, T 22 20 063.172 cm 1, and T 33 20 066.248 cm 1 and then they turn back to lower wave numbers with T 44 20 060.687 cm 1, T 55 20 047.327 cm 1, and T 66 20 028.759 cm 1. The origins of the 2–2, 3–3, and 4–4 bands are separated only by a few wave numbers so that extensive overlapping of lines occurs. In particular, the 4–4 Q branch is overlapped almost completely by the stronger 2–2 and 3–3 Q branches, and we were able to observe only some ten 4–4 Q lines at low N values. The 5–5 and 6–6 Q branches also present some interesting aspects caused by the slightly different vibrational dependence of the B v values in the A and X states. The B – B difference is initially positive for the 0–0 band, decreases to zero for the 5–5 band, and becomes slightly negative for the 6–6 band. This fact results in a sharp Q head at 20 047.5 cm 1 for the 5–5 band, with the first ten Q lines unresolved. The observation of Q lines and of the first P and R lines in the 4–4 and 5–5 bands allowed us to determine reliable band origins of 20 060.687 cm 1 4–4 and 20 047.327 cm 1 5–5 instead of the previous estimates of 20 062.56 cm 1 4–4 and 20 052.05 cm 1 5–5 based only on P and R lines.20 The 6–6 Q branch displayed in Fig. 2 presents a very interesting appearance. The B difference is so small than the two spin components behave differently, with the Q 1 lines starting at Q 1 (N 1) 20 029.258 cm 1 and going to decreasing wave numbers with increasing N. In contrast, the Q 2 lines start at Q 2 (N 1) 20 027.657 cm 1, go to higher wave numbers to form a head at 20 028.22 cm 1 (N 3), and then turn back to lower wave numbers. The two Q branches unresolved at high N values then form an ‘‘extra’’

head at 20 019.3 cm 1 (N 24) and return to higher wave numbers as N increases further. as The A 2 state is strongly perturbed by the C 2 –X 2 noted by Colin et al. in their analysis of the C 2 system.20 Indeed these perturbations were used to connect state and the high vibrational levels of the ground the C 2 state with the v 0 level of the X 2 state. Colin et al. found that the v 0, 1, and 2 vibrational levels of the C 2 state were interacting with the v 4, 5, 6, and 7 vibrational spectrum, we levels of the A 2 state. In our A 2 – X 2 have observed strongly perturbed P and R lines in the 2–2 to 6–6 bands, while for the 0–0 and 1–1 bands only a few perturbed P and R lines were assigned in the region of the heads. No local perturbations were found in any of the Q branches. For example, one can see that the 6–6 Q branch displayed in Fig. 2 exhibits no local perturbations up to N 24, although the P and R lines are already strongly perturbed at N 11. This fact may be explained by the different interaction of the four (F 1 e/ f and F 2 e/ f energy levels of a given N of the A 2 state with the two (F 1 e and F 2 f levels state. of the C 2 The selection rules for perturbations are J 0, e – e, and f – f so that only the e level of the F 1 spin component and the f level of the F 2 component of the A 2 state are perturbed for a N 0 interaction with the C 2 state. In this case the Q 2 e – f and Q 1 f – e branches will not be perturbed. In principle, N 1 interactions are possible and they would lead to perturbed Q branches. Experimentally no such perturbed Q branches were detected because the A 2 state belongs to Hund’s case b . N is therefore a good quantum number for both rotations and perturbations so that the N 1 interactions become very weak. In order to derive the vibrational intervals, the analysis of a previously recorded20 arc emission spectrum of the A 2 –X 2 1 sequence was carried out. The 0–1 v to 6–7 bands were identified in the 17 800–19 000 cm 1 spectral region. Because of the positive B – B difference, which is greater than in the v 0 sequence, the v 1 bands form ‘‘classical’’ P heads. These heads are clearly

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J. Chem. Phys., Vol. 109, No. 14, 8 October 1998 TABLE I. Effective constants in cm uncertainties are 1 .a
v
1

Focsa et al.
2

for the vibrational levels of the X

ground state of BeH all

Tv 0 1 986.4442 103 3 896.8785 185 5 729.2861 312 7 480.4528 438 9 145.2834 730 10 716.2804 878 12 182.323 117 13 525.889 123 14 717.860 124 15 709.040 137

Bv 10.164 888 0 739 9.855 433 5 630 9.541 727 1 869 9.220 768 100 8.886 639 123 8.533 209 248 8.152 609 264 7.729 457 898 7.230 85 128 6.592 13 182 5.698 37 219 1.810(115) 10
16

D v 103 1.022 969 162 1.014 180 125 1.010 671 228 1.010 356 320 1.017 254 500 1.034 38 154 1.074 28 213 1.213 79 463 1.462 02 863 1.913 4 193 2.758 5 148 cm
1

H v 107 0.959 35 159 0.941 908 948 0.937 35 233 0.903 43 403 0.827 62 785 0.628 5 349 0.327 8 593 1.756 3 875 4.276 215 11.600 782 ¯

L v 1011 0.982 01 704 1.074 58 237 1.358 87 782 1.765 0 163 2.388 4 397 2.993 251 4.425 524 27.60 538 83.93 177 333.0 105 ¯

0 1 2 3 4 5 6 7 8 9 10
a

An additional parameter M

was determined for the v 0 level.

visible in the case of the 0–1 to 3–4 bands but for the 4–5, 5–6, and 6–7 bands they become less prominent as the intensity decreases. The weakness of these lines, along with overlap by stronger Q and R lines of the lower v bands, made the assignment of the 4–5, 5–6, and 6–7 bands very difficult. In addition, the v 4, 5, and 6 vibrational levels of the A 2 state begin to be perturbed at low N values 24, 16, and 11 for v 4, 5, and 6, respectively and the corresponding P and R lines are displaced. Fortunately, the Q lines are not perturbed and we were able to follow the Q branches to higher N values than the P and R branches. The presence of 1 sequence these well-behaved Q branches in the v added some new information to our data set because the high v bands of the v 0 Fourier transform spectroscopy FTS measurements had only partly resolved Q branches.
B. Theoretical model and least-squares treatment

ˆ We used the usual effective N2 Hamiltonian for 2 and 25 states to reduce the experimental data to molecular constants. Explicit matrix elements for 2 and 2 states are provided in Refs. 26 and 27. Because of the extensive amount of high quality data, we needed to use higher-order constants such as M in the X 2 v 0 level or -doubling parameters up to q L in some of the vibrational levels of the A 2 state. The matrix elements corresponding to these parameters were calculated by matrix multiplication e.g., qH (Dq qD)/2 . The experimental lines and the ground state combination differences see below were fitted using a nonlinear, leastsquares procedure with each datum weighted with the square of the reciprocal of the estimated uncertainty. The unblended FTS lines were assigned a weighting factor of 0.01 cm 1, 1 data were weighted at 0.05 cm 1 for the while the v strongest lines and 0.1 cm 1 for the weaker ones. However, the measurements of the blended lines were very imprecise in the arc emission spectrum and they were heavily deweighted in the fits. The main goal of this initial work is a complete characterization of the X 2 ground state, so the perturbed lines in the v 0 sequence were heavily deweighted but the corresponding ground state combination differences were included in the fits. The inclusion of these combination differ2

ences greatly improved our determination of the ground state constants and helped to uncouple the two electronic states. They also served as a check for our rotational assignments. We intend to carry out a thorough deperturbation of the states at a later date. A 2 and the C 2 The main fitting strategy was to work with the v 0 FTS bands first and then use these rotational constants in the 1 fits, allowing only the band origins to vary. This v strategy was applied for the 0–0 to 4–4 and the 0–1 to 3–4 bands. However, the 4–4, 5–5, and 6–6 bands have peculiar Q branches that were compact and difficult to assign. It 1 bands turned out that although the Q lines in the v were of lower precision they could be followed to higher N for the 4–5, 5–6, and 6–7 bands than in the 4–4, 5–5 and 6–6 bands. Consequently, we decided to fit all of these bands together and to determine the parameters of the A 2 ( v 4, 5, and 6 and X 2 ( v 5, 6, and 7 levels simulta( v 4) level were neously the constants for the X 2 kept fixed at the values determined from the 4–4 fit . These fits gave more reliable values for the -doubling parameters in the A 2 upper state. The assignment of the 6–7 band linked together the lower vibrational levels ( v 0 – 6) of the ground state with data on the higher vibrational levels, v 7 – 10, derived –X 2 study.20 Because the C 2 from the C 2 v 0, 1, and 2 levels are massively perturbed, only the ground state combination differences were introduced into our fit. In addition to the usual rotational differences, all the possible differences between P lines and R lines with the same N , N , and v but different v were added to the fit in order to vibrational intervals. In this way, the viobtain the X 2 brational energy levels for v 4 – 10 of the ground state were fitted together. The output of this fit, as well as the outputs of the band-by-band fits, has been placed in Physics Auxiliary Publication Service PAPS .28 The molecular constants obtained are presented in Tables I and II for the and A 2 states, respectively. X 2 electronic state it was possible to In the ground X 2 determine the rotational constants B, D, H, and L except for v 10 where limited data gave only B and D Table I . An M constant was also required for v 0. A similar set of rotational parameters Table II were required for the A 2 state

J. Chem. Phys., Vol. 109, No. 14, 8 October 1998

TABLE II. Molecular constants in cm Constant T v0 Bv D v 103 H v 107 L v 1011 Av 3 v 10 106 Dv q v 102 q D v 106 q H v 109 q L v 1013
a

1

for the vibrational levels of the A
v

2

state of BeH all uncertainties are 1 .a
v

v

0

1

2

v

3

v

4

v

5

v

6

20 030.962 73 233 10.302 101 4 697 1.042 986 123 0.924 517 852 0.949 73 197 2.154 3 142 7.778 295 7.790 504 1.402 65 284 6.217 8 800 1.408 7 697 3.002 190
H

22 037.754 9 124 9.970 041 6 643 1.039 877 141 0.917 84 123 1.130 82 376 2.132 5 126 5.955 194 3.588 193 1.348 99 381 6.656 137 1.814 158 5.810 578
9

23 960.042 1 209 9.631 231 9 885 1.041 220 252 0.913 97 291 1.419 4 115 2.185 7 164 8.146 252 6.504 314 1.266 34 496 6.758 233 2.118 346 1.247 163

25 795.566 9 339 9.281 843 111 1.045 716 468 0.914 17 853 2.113 5 538 2.223 9 157 8.760 333 8.451 669 1.191 28 268 7.091 6 540 ¯ ¯

27 541.093 7 493 8.918 924 166 1.050 190 985 0.810 2 286 3.296 270 2.171 5 184 8.094 618 6.45 175 1.143 5 213 12.774 465 ¯ ¯

29 192.634 1 731 8.539 357 258 1.069 94 124 0.414 5 138 ¯ 2.248 3 319 5.031 727 ¯ 1.103 1 339 25.71 176 ¯ ¯

30 745.046 4 880 8.141 314 257 1.163 90 180 0.264 2 142 ¯ 2.194 4 242 4.461 344 ¯ 1.193 6 246 157.96 268 ¯ ¯

An additional parameter

2.220(198) 10

cm

1

was determined for the v 0 level.

TABLE III. Dunham constants in cm m 0 Y 0,m Y 1,m Y 2,m Y 3,m Y 4,m Y 5,m Y 6,m Y 7,m Y 8,m 2068.863 4 5174 46.145 5 6352 4.980 9 3694 1.612 0 1167 0.289 17 2120 3.097 8(2210) 10 1.783 9(1228) 10 3 4.445 3(2817) 10

1

for the X

2

ground state of BeH all uncertainties are 1 . m 1 m 2 1.044 176 0 6760 10 6.654 3 2154 10 5 5.964 6 2101 10 5 2.657 77 8897 10 5 6.006 1 1813 10 6 6.434 1 1733 10 7 2.608 59 6180 10 8
3

m 3 1.024 361 3302 10 2.174 24 8582 10 8 2.023 18 7169 10 8 7.807 2 2579 10 9 1.385 47 4124 10 9 9.749 9 2338 10 11
7

m 4 9.539 09 8802 10 1.042 1000 10 13 9.289 4 3947 10 13
12

m 5 1.6404(1326) 10
16

2

10.331 214 7 5042 0.351 068 1721 4.833 4 1856 10 2 2.527 35(9045) 10 2 6.668 9(2266) 10 3 9.657 1(3021) 10 4 7.065 8(2031) 10 5 2.102 43(5411) 10 6

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Focsa et al. state of

TABLE IV. Main equilibrium constants in cm BeHa,b all uncertainties are 1 .

of the A

2

T e 20 019.7647(146) 2089.953 0(421) B e 10.466 305(273) e x e 41.363 9(303) e 0.327 746(405) 0.074 83(766) 0.001 237(157) ey e 1e 0.037 98(617) 0.000 519 3(166) ez e 2e
e a

b

Gv e( v 2) Bv Be e( v

1

ex e( v

1 2)

1 2 2)

ey e( v

1e ( v

1 2 2)

2e ( v

1 3 2) 1 3 2) .

ez e( v

1 4 2) .

along with the -doubling series q, q D , q H , and q L as well as the spin–orbit coupling constant A and the spin–rotation constants and D . The A 2 and X 2 electronic states of BeH both belong to the Hund’s case b coupling case, and this led to strong correlation between the spin–rotation parameters and . No satellite branches were detected so could not be directly determined. We have therefore chosen to fix the ground state constant to zero and to vary the corresponding constant in the upper state. The -doubling constant p also could not be determined because of the nearly pure case b coupling in the A 2 state. A second stage in our analysis was to fit all the available data together, including the vibrational levels v 0 to 10 for the X 2 state and v 0 – 6 for the A 2 state in a global fit to determine Dunham constants29 in the ground state. In this case, the ground state rovibrational energies were represented by the conventional double Dunham expansion,29 E X v ,N Y l,m v 1 2
l

FIG. 3. A plot of of BeH.

Gv

1/2

as a function of v for the A

2

and X

2

states

N N

1

m

,

1

l,m

and the upper A 2 levels were represented by the same 2 matrix discussed above. The values of the Y l,m parameters obtained are listed in Table III. However, it should be noted that the normalized standard deviation of 1.8 of this fit was somewhat higher than the values of about 1 obtained in the separate fits described above. The equilibrium vibrational and rotational constants were also derived for the A 2 state using the constants listed in Table II and the equilibrium parameters are presented in Table IV.
IV. DISCUSSION

these extra two Q heads turn out to belong to the 6–6 and 7–7 bands, but Watson and Parker were clearly on the right track. The various parameters Table II in the excited A 2 state empirically account for the observed spectroscopic features. The long series of -doubling parameters q’s are necessary because the Q branches connect to excited state rotational levels of opposite parity compared to the P and R branches. This leads to a combination defect between the Q branches and the P and R branches that would normally be state is nearby and the strong small. In this case the C 2 local interactions require as many q parameters as there are terms in the B series of parameters. The q series of parameters thus lets the e and f parity levels have slightly different effective rotational constants. The spin splitting is resolved only at low N values and disappears as the spin uncoupling becomes complete. This splitting is represented in the A 2 state by the spin–orbit coupling constant A and the two spin–rotation constants and D . Since A D and are completely correlated30 for a 2 state, we have chosen to determine because the A 2 state is close to Hund’s case b . The effect of the constants and

The new Fourier transform spectra of the A 2 – X 2 system greatly improved the spectroscopic constants and also cleared up some spectroscopic mysteries. One puzzling feature in the spectra was the appearance of two groups of unassigned lines to lower wave numbers of the strong 0–0 Q branch. They are the tiny features on the left-hand side of the 0–0 Q branch in Fig. 1 see also Fig. 2 . These lines look like peculiar Q branches and they were noted even in early arc spectra of Watson and Parker.12 In fact the presence of many additional P and R lines in the A 2 – X 2 transition led Watson and Parker to the erroneous conclusion that they had found the 8BeH isotopomer. They understood that the A – X system had a head-of-heads at the 4–4 band and they assigned the two extra Q branches to the 8–8 and 9–9 bands. The head-of-heads in fact forms at the 3–3 band and

FIG. 4. A plot of B v as a function of v for the A BeH.

2

and X

2

states of

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FIG. 5. The RKR potential energy curves for the A BeH.

2

and X

2

states of

D is to allow the F 1 and F 2 spin components to have slightly different effective B values while the A constant, as usual, is the rotationless spin–orbit splitting. Since we have arbitrarily set the spin–rotation constant to zero in the ground state, the exited state constant is, – . In this respect the in fact, the difference A 2 –X 2 transition is like a 2 – 2 transition. It is pos2(2) 10 3 cm 1 for the sible to estimate a value of ground state using Curl’s relationship,31,32 2B g, and the small anisotropy of the g tensor of matrix-isolated BeH.33 A crude estimate based on a pure precession relationship34 between the ground state and the A 2 state gives a similar 4 10 3 cm 1. Note that pure precession also value of implies that the experimentally undetermined -doubling pa) has the same value of 4 10 3 cm 1 in the rameter p ( 2 A state. states have remarkably similar The A 2 and X 2 vibrational and rotational constants as is illustrated graphically in Figs. 3 and 4. In Fig. 3, G 1/2 G 1/2 and the diagonal bands go to higher wave numbers as v increases but a head-of-head forms when the difference in G v 1/2 values becomes negative after the 3–3 band. In the B v plot Fig. 4 , the excited state B v values are initially greater than in the ground state for the diagonal bands and the Q branches go to higher wave numbers as N increases Fig. 1 . At the 5–5 band, however, the ground and excited state B v values become identical Fig. 4 and a linelike Q branch results, although because of centrifugal distortion some lines are resolved at higher N values in the hotter spectrum. The peculiar 6–6 Q branch Fig. 2 has already been discussed.

The Dunham constants of Table III are a poor representation of the energy levels of BeH. This is a well-known fact for hydrides8 and is a particular problem for H2. The traditional constants form a badly convergent series with strong correlation between the parameters. It is, therefore, necessary to carry many extra significant figures in Table III and many of the terms even e ) in the expansion have lost much of their physical meaning. Nevertheless, the Y’s of Table III do reproduce the experimental data in an empirical manner. In future work, we plan to explore the fitting of the BeH and BeD data using alternate energy level expressions35 as well as the direct fitting to a potential energy curve that includes Born–Opppenheimer breakdown terms.36 The B v (Y i1 ) and G v (Y i0 ) functions Table III were used to calculate the Rydberg–Klein–Rees RKR potential energy curve plotted for the ground state shown in Fig. 5. As can be seen in Fig. 5, v 10 is the last bound vibrational level although it is difficult to rule out37 a v 11 level bound by a few cm 1. Interestingly, the outer turning points of v 9 and 10 are not in the long-range region so a LeRoy– Bernstein analysis38 of the G v data Fig. 3 is not appropriate. The A 2 excited state rotational constants and band origins Table II were fitted with the traditional expressions Table IV to obtain equilibrium constants. The equilibrium bond length for the A 2 state was calculated to be 1.332 99 2 Å compared to 1.341 68 3 Å for the ground state, calculated from Y 01 Table III . The equilibrium constants of Table IV were used to calculate the A 2 state RKR potential curve also displayed in Fig. 5. The RKR turning points are available from the authors upon request. The RKR potential energy curves were used to calculate the Franck–Condon factors Table V . A glance at Table V 1 sequence explains why we were not able to see the v in spite of the excellent signal-to-noise ratio Fig. 1 obtained 1 bands, the largest for v 0 bands. For the v Franck–Condon factor is 0.0042 for the 2–3 band so that we were forced to use the older arc measurements to see the bands. Note that since we only used the v 1 sequence, all of the systematic errors in the calibration of the photographic plates propagate upwards so that the v 10 level could be in error by as much as 2 cm 1.
V. CONCLUSION

We have measured the 0–0 to 6–6 bands of the A 2 –X 2 transition of BeH with a Fourier transform spectrometer. These bands show many unusual features such

TABLE V. Franck–Condon factors for the A
v v

2

–X

2

transition of BeH. 3 4 6 4 3 3 4 6 4.42E 3.57E 3.47E 3.96E 0.992 3.42E 7.06E 8 6 4 3 3 4 5 5.86E 4.36E 1.05E 5.74E 3.09E 0.993 2.10E 9 5 5 4 3 3 6 7.26E 7.49E 1.04E 2.56E 8.24E 1.85E 0.995 6 7 7 5 4 3 7 8.56E 8.23E 9.65E 4.04E 5.41E 1.07E 5.44E 6 6 6 4 5 3 4 8 4.24E 1.27E 2.11E 2.79E 1.66E 9.70E 1.38E 9 5 5 5 6 5 3 9 1.17E 1.11E 2.24E 6.18E 3.80E 7.38E 1.35E 6 5 5 5 5 6 4 10 1.72E 6.57E 1.86E 5.32E 1.33E 4.14E 1.97E 7 6 5 5 4 5 5

0 0.998 2.09E 2.05E 2.73E 5.63E 1.55E 8.07E 3 5 5 7 6 6

1 2.07E 0.994 3.72E 8.00E 2.86E 5.10E 9.89E 3 3 5 5 5 6

2 5.00E 3.59E 0.992 4.41E 2.10E 6.44E 2.35E 5 3 3 4 04 04

0 1 2 3 4 5 6

1.11E 1.69E 4.18E 0.991 4.27E 4.23E 5.10E

5802

J. Chem. Phys., Vol. 109, No. 14, 8 October 1998
16 17

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as a head-of-heads and peculiar Q branches as the result of the near identity of the spectroscopic constants in the two 1 states. By assigning the 0–1 to 6–7 bands in the v sequence in an archival arc emission spectrum, we were able to link together all of the new FTS data as well as connect with the C 2 –X 2 bands which cover v 7 – 10. BeH thus joins the small set of chemically bound molecules for which all of the ground state vibrational levels have been derived from high-resolution data.
ACKNOWLEDGMENTS

This work was supported by the Fonds National de la Recherche Scientifique Belgium and the Natural Sciences and Engineering Research Council of Canada. C.F. thanks ´ the Universite des Sciences et Technologies de Lille France for a BQR grant. We thank R. LeRoy, M. Carleer, and R. Mitzner for their help and for discussions.
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